CN107022241B

CN107022241B - Nano-silver and gelatin modified antibacterial ink and preparation method thereof

Info

Publication number: CN107022241B
Application number: CN201710325927.6A
Authority: CN
Inventors: 黄雅钦; 李静慧
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2017-05-10
Filing date: 2017-05-10
Publication date: 2020-09-04
Anticipated expiration: 2037-05-10
Also published as: CN107022241A

Abstract

The invention relates to nano-silver and gelatin modified antibacterial ink and a preparation method thereof, wherein the nano-silver and gelatin modified antibacterial ink comprises the following ingredients in parts by weight: 10 portions of black carbon powder, 60 to 540 portions of gelatin solution, 0.0025 to 1.8 portions of silver salt, 0.0015 to 0.9 portion of reducing agent, 0.5 to 10 portions of emulsifying agent, 0.5 to 15 portions of wetting agent and 0 to 1 portion of spice. The prepared antibacterial ink has strong antibacterial property, is nontoxic and odorless, and is suitable for large-scale popularization and application.

Description

Nano-silver and gelatin modified antibacterial ink and preparation method thereof

Technical Field

The invention relates to nano-silver and gelatin modified antibacterial ink and a preparation method thereof, belonging to the field of painting and calligraphy tools.

Background

In the traditional art of China, calligraphy occupies a very important position and has the characteristics of Chinese nationality. The ink of one of four treasures of the study, which is closely related to the calligraphy, has a long history of use, which can be traced back thousands of years ago. As an indispensable art performance article in the field of Chinese art, the performance of the ink is improved continuously, is improved and is further inherited, and the ink is bright.

A plurality of ink is sold in the market at present, the variety is various, the ink is basically made of carbon black and animal sizing materials, and the sizing materials are easy to decay, so that in order to prevent the ink product from deteriorating, toxic substances such as phenol and xylenol are added to be used as preservatives to inhibit the growth of bacteria, and the storage of the ink is prolonged. The addition of such preservatives makes the ink less safe and smelly, and the long-term use, inhalation and discharge after use will certainly have adverse effects on the human body and the environment. In the field of the prior art, a plurality of patents about ink products exist, but most of the patents focus on the research on the problems of improvement of the brightness of ink and the like. The problem of replacing preservatives such as phenol in the ink and thereby improving the antibacterial safety of the ink is not significantly improved.

Compared with bone glue, the gelatin has more precise preparation process and better gluing and dispersing effects. The nano silver has obvious inhibiting and killing effects on dozens of pathogenic microorganisms such as escherichia coli, staphylococcus aureus, chlamydia trachomatis and the like, has broad-spectrum sterilization and no drug resistance, has no toxic reaction on the growth of cells, has no stimulation on skin, and is widely applied to the fields of food packaging, medical manufacturing, green household appliances and the like. However, the simultaneous application of the nano silver and the gelatin to the modification of the ink has not been reported.

Disclosure of Invention

The invention provides nano-silver and gelatin modified antibacterial ink and a preparation method thereof, aiming at the problems of low biological safety, large odor and the like of the existing ink products such as ink and the like.

The invention adopts the following technical scheme: the nano-silver and gelatin modified antibacterial ink comprises the following ingredients in parts by weight:

the ink-carbon powder 10 is mixed with the ink-carbon powder,

the gelatin solution is 60-540, and the gelatin solution is,

0.0025 to 1.8 parts of silver salt,

0.0015 to 0.9 percent of reducing agent,

0.5-10 parts of emulsifier,

0.5-15 parts of wetting agent,

0-1 part of perfume.

Wherein, the ink carbon powder can be selected from various carbon blacks in the prior art.

In a preferred embodiment of the invention, the part by weight of the gelatin solution is 240-420, more preferably 300-360, and the concentration of the gelatin solution is 1-2 wt%.

In a preferred embodiment of the present invention, the gelatin is a gelatin prepared by extraction from connective tissues such as skin, bone, achilles tendon or scales of animals.

In a preferred embodiment of the invention the part by weight of silver salt is 0.1 to 0.7, more preferably 0.12 to 0.3, said silver salt being selected from one or more of silver nitrate or silver ammonia.

In a preferred embodiment of the present invention, the reducing agent is selected from the group consisting of ascorbic acid, sodium borohydride, hydrated amine, sodium citrate, glucose or hydrogen peroxide, more preferably ascorbic acid, in an amount of 0.05 to 0.35, more preferably 0.06 to 0.15 parts by weight.

In a preferred embodiment of the invention the emulsifier is present in an amount of 4 to 8, more preferably 5.5 to 7.5 parts by weight, said emulsifier being selected from turkish red oil.

In a preferred embodiment of the invention, the part by weight of humectant is from 1 to 8, more preferably from 2 to 4, said humectant being selected from glycerol, trimethylolpropane or 1,2, 4-butanetriol, more preferably glycerol.

In a preferred embodiment of the present invention, the part by weight of the perfume is 0.05 to 0.5, more preferably 0.08 to 0.1, and the perfume is selected from one or more of camphor oil, borneol fine powder and camphor powder.

The invention also provides a preparation method of the antibacterial ink, which comprises the following steps:

1) dissolving gelatin in water to prepare 1-2wt% gelatin water solution;

2) dissolving silver salt in a proper weight part ratio into the gelatin solution in the step 1) in a proper weight part ratio, and uniformly stirring;

3) dissolving ascorbic acid or sodium borohydride in a proper weight part ratio in the gelatin solution in the step 1 in a proper weight part ratio, uniformly stirring, and adjusting the pH = 5-11;

4) slowly dripping the uniformly stirred ascorbic acid solution into the uniformly stirred silver nitrate solution, stirring at the temperature of 30-80 ℃, and reacting for 0.5-4h to prepare a nano silver solution;

5) taking ink carbon powder, and grinding the ink carbon powder into fine carbon powder for later use;

6) slowly adding fine carbon powder in a proper weight part ratio into the nano silver solution after the reaction is finished, and continuously stirring to uniformly disperse the fine carbon powder;

7) adding spice, an emulsifier and a wetting agent in a proper weight part ratio into the mixture, stirring again to fully mix the mixture, and grinding the mixture to be fine and uniform to obtain the antibacterial ink.

In a preferred embodiment of the invention, the pH of step 3) is 9.5.

In a preferred embodiment of the present invention, the reaction temperature of step 4) is 60 ℃ and the reaction time is 1.5 h.

In a preferred embodiment of the present invention, the grinding is performed by ball milling or hand milling in a mortar.

Compared with the prior art, the invention has the following advantages:

1) according to the nano-silver antibacterial ink provided by the invention, gelatin is used as an auxiliary agent to synthesize nano-silver, and then the nano-silver antibacterial ink is prepared, so that the problem that the gelatin is highly nutritional and is easily infected by bacteria is effectively solved, the antibacterial property of the prepared ink is greatly improved, and compared with the traditional ink, the prepared ink is unpleasant in smell and toxic due to the biological safety of the nano-silver, the prepared ink is non-toxic and odorless, and the use safety is high. The preparation process adopts ball milling and mortar hand milling processes, so that the fineness of carbon black particles in the ink is effectively controlled, the preparation process is green and environment-friendly, and the preparation process is simple. The prepared nano silver ink has the characteristics of black and bright ink marks, strong layering sense, difficult ink leakage and smooth writing while the antibacterial safety of the ink is improved and the smell is improved.

2) In the preparation of the ink, gelatin is used as an adhesive and a dispersing agent, so that carbon black particles can be better fixed when permeating into paper or other substances during writing, the ink is effectively prevented from falling off, and the ink is prevented from being easily precipitated in a short time after being ground and diluted into liquid. In addition, the gelatin also plays a role in lubricating writing and improving the gloss of writing in the ink manufacturing process. However, due to the high nutrition of the gelatin, the gelatin is easily eroded by bacteria, and the prepared ink is easily rotten and deteriorated.

3) The preparation process adopts ball milling and mortar hand milling processes to effectively control the fineness of the ink carbon powder, so that the writing after the ink is written is firmly attached to the paper and ink is not easy to run. The ink disclosed by the invention is simple in preparation process, green and environment-friendly in preparation process, and has the characteristics of strong blackness of ink marks, strong layering, smoothness and smoothness in writing, easiness in drying after writing and difficulty in ink leakage while improving the safety and the smell of the traditional ink.

The blackness of the existing part of commercially available ink tested by a reflection densimeter is only about 1.35, ink leakage can occur after the ink is soaked for 6 hours, the smell of the ink is large, and the antibacterial test result is poor. The anti-bacterial ink has the advantages that the black degree is larger than 1.47 in a reflection densitometer test, ink does not run for 6 hours or even 12 hours after the written handwriting is subjected to a water immersion experiment, the ink is non-toxic and odorless, and the anti-bacterial test effect is good. According to the regulation in the national standard QB/T2860-2007, the invention can be far superior to the standard requirement.

Drawings

The invention is further described below with reference to the accompanying drawings:

FIG. 1 is a comparison graph of an antibacterial experiment of inhibiting escherichia coli for 36 hours by using self-made gelatin ink, commercially available ink and the nano-silver and gelatin modified antibacterial ink of the invention;

wherein a is a home-made gelatin ink, b is a commercially available ink, and c is the antibacterial ink of example 1.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.

Example 1:

1) dissolving gelatin in water to prepare a gelatin water solution with the concentration of 2wt% for later use;

2) dissolving silver nitrate in a weight part ratio of 0.3 in the gelatin solution in the step 1) in a weight part ratio of 180, and uniformly stirring;

3) dissolving 0.15 parts by weight of ascorbic acid in 180 parts by weight of the gelatin solution obtained in the step 1), uniformly stirring, and adjusting the pH to be = 9.5;

4) slowly dripping the uniformly stirred ascorbic acid solution into the uniformly stirred silver nitrate solution, magnetically stirring at 60 ℃, and reacting for 1.5h to prepare a nano silver solution;

5) taking 10 parts by weight of ink carbon powder, and grinding the ink carbon powder into fine carbon powder for later use;

6) slowly adding the fine carbon powder into the nano silver solution after the reaction is finished, and continuously stirring to uniformly disperse the fine carbon powder;

7) adding 0.1 part by weight of borneol fine powder, 6 parts by weight of Turkey red oil and 4 parts by weight of glycerin into the mixture, stirring again to fully mix the materials, and grinding the materials to be fine and uniform to obtain the antibacterial ink.

The prepared ink has no peculiar smell and good antibacterial effect; the blackness is 1.61 by a reflection densimeter; after writing, a water immersion test is carried out for 12 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor.

Example 2:

2) dissolving silver nitrate in a weight part ratio of 1.35 in the gelatin solution in the step 1) in a weight part ratio of 270, and uniformly stirring;

3) dissolving 0.7 parts by weight of ascorbic acid in 270 parts by weight of the gelatin solution obtained in the step 1), uniformly stirring, and adjusting the pH to be = 10;

4) slowly dripping the uniformly stirred ascorbic acid solution into the uniformly stirred silver nitrate solution, magnetically stirring at 70 ℃, and reacting for 1h to prepare a nano-silver solution;

7) adding 0.05 part by weight of camphor oil, 3 parts by weight of Turkey red oil and 8 parts by weight of glycerol into the mixture, stirring again to fully mix the materials, and grinding the materials to be fine and uniform to obtain the antibacterial ink.

The prepared ink has no peculiar smell and good antibacterial effect; the blackness is 1.54 by a reflection densimeter; after writing, a water immersion test is carried out for 12 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor.

Example 3:

2) dissolving silver nitrate in 0.005 part by weight into the gelatin solution in the step 1) in 60 parts by weight, and uniformly stirring;

3) dissolving 0.0025 parts by weight of ascorbic acid into 60 parts by weight of the gelatin solution in the step 1), uniformly stirring, and adjusting the pH to be = 9;

4) slowly dripping the uniformly stirred ascorbic acid solution into the uniformly stirred silver nitrate solution, magnetically stirring at 50 ℃, and reacting for 2 hours to prepare a nano silver solution;

7) adding 0.5 parts by weight of camphor powder, 4 parts by weight of Turkey red oil and 0.5 parts by weight of 1,2, 4-butanetriol into the mixture, stirring again to fully mix the materials, and grinding the materials to be fine and uniform to obtain the antibacterial ink.

The prepared ink has no peculiar smell and good antibacterial effect; the blackness is 1.48 by a reflection densimeter; after writing, a water immersion test is carried out for 10 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor.

Example 4:

1) dissolving gelatin in water to prepare 1.5wt% gelatin water solution for later use;

2) dissolving silver nitrate in a weight part ratio of 0.3 in the gelatin solution in the step 1) in a weight part ratio of 150, and uniformly stirring;

3) dissolving 0.075 part by weight of sodium borohydride in 150 parts by weight of the gelatin solution in the step 1), uniformly stirring, and adjusting the pH to be = 8.5;

7) adding 0.08 parts by weight of camphor oil, 6 parts by weight of emulsifier and 3 parts by weight of wetting agent into the mixture, stirring again to fully mix the components, and grinding the mixture to be fine and uniform to obtain the antibacterial ink.

The prepared ink has no peculiar smell and good antibacterial effect; the blackness is 1.47 by a reflection densimeter; after writing, a water immersion test is carried out for 8 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor.

Example 5:

2) dissolving silver nitrate in 0.15 part by weight into the gelatin solution in the step 1) in 180 parts by weight, and uniformly stirring;

3) dissolving 0.04 part by weight of sodium borohydride into 180 parts by weight of the gelatin solution in the step 1), uniformly stirring, and adjusting the pH = 9;

4) slowly dripping the uniformly stirred ascorbic acid solution into the uniformly stirred silver nitrate solution, magnetically stirring at 65 ℃, and reacting for 1h to prepare a nano-silver solution;

7) adding 0.1 part by weight of borneol fine powder, 8 parts by weight of emulsifier and 6 parts by weight of wetting agent into the mixture, stirring again to fully mix the materials, and grinding the materials to be fine and uniform to obtain the antibacterial ink.

The prepared ink has no peculiar smell and good antibacterial effect; the blackness is 1.47 by a reflection densimeter; after writing, a water immersion test is carried out for 6 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor.

Fig. 1 is a comparison graph of a self-made gelatin ink, a commercially available ink and the nano silver and gelatin modified antibacterial ink of the invention after 36h of an antibacterial experiment for inhibiting escherichia coli, and the growth conditions of colonies can show that the self-made ink without adding silver salt has no antibacterial property and more colonies grow, the commercially available ink grows slower than the colonies of the self-made ink without adding silver salt, but still has colonies growing, the antibacterial effect is poor, and the nano silver and gelatin modified antibacterial ink of the invention has no obvious colony growth observed and has good antibacterial effect.

The prepared ink in the examples 1-5 has no peculiar smell, and has very good antibacterial effect; testing the blackness by a reflection densimeter to be more than 1.47; after writing, a water immersion test is carried out for 6 hours or even 12 hours without ink leakage; can achieve the effects of strong blackness, difficult ink leakage, easy drying after writing, no toxicity and no odor. And the black degree of the ink sold in the market is only about 1.35 by using a reflection densimeter, the ink runs out after the ink is soaked for 6 hours, the smell of the ink is large, and the antibacterial test effect is poor.

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.

Claims

1. The preparation method of the nano-silver and gelatin modified antibacterial ink is characterized by comprising the following ingredients in parts by weight:

ink carbon powder 10;

60-540 parts of gelatin solution;

silver salt 0.0025-1.8;

0.0015 to 0.9 percent of reducing agent;

0.5-10 parts of emulsifier,

0.5-15 parts of wetting agent;

0-1 part of spice;

1) dissolving gelatin in water to prepare 1-2wt% gelatin solution for use;

3) dissolving a reducing agent in a proper weight part ratio in the gelatin solution obtained in the step 1), uniformly stirring, and adjusting the pH = 5-11;

4) slowly dropping the uniformly stirred solution in the step 3) into the uniformly stirred solution in the step 2), stirring at 30-80 ℃, and reacting for 0.5-4h to prepare a nano silver solution;

2. The method according to claim 1, wherein the gelatin solution is used in an amount of 240 parts by weight and 420 parts by weight, and the concentration of the gelatin solution is 1-2 wt%.

3. The method according to claim 2, wherein the gelatin solution is 300-360 parts by weight.

4. The method according to claim 1, wherein the gelatin is a gelatin extracted from skin, bone, achilles tendon or scale of an animal.

5. The method according to claim 1, wherein the silver salt is 0.1 to 0.7 part by weight, and the silver salt is one or more selected from silver nitrate and silver ammonia.

6. The method according to claim 5, wherein the silver salt is used in an amount of 0.12 to 0.3 parts by weight.

7. The method according to claim 1, wherein the reducing agent is selected from ascorbic acid, sodium borohydride, hydrated amine, sodium citrate, and glucose in an amount of 0.05 to 0.35 parts by weight.

8. The method according to claim 7, wherein the reducing agent is ascorbic acid in an amount of 0.06 to 0.15 parts by weight.

9. The method according to claim 1, wherein the emulsifier is selected from the group consisting of turkish red oil in an amount of 4 to 8 parts by weight.

10. The method according to claim 9, wherein the emulsifier is present in an amount of 5.5 to 7.5 parts by weight.

11. The method of claim 1, wherein the humectant is selected from the group consisting of glycerin, trimethylolpropane, and 1,2, 4-butanetriol in an amount of 1 to 8 parts by weight.

12. The method of claim 11, wherein the humectant is 2 to 4 parts by weight and the humectant is glycerin.

13. The method according to claim 1, wherein the perfume is selected from one or more of camphor oil, borneol fine powder and camphor powder in an amount of 0.05-0.5 parts by weight.

14. The method of claim 13, wherein the perfume is used in an amount of 0.08 to 0.1 parts by weight.

15. The preparation method of claim 1, wherein the pH value in the step 3) is 9.5, the reaction temperature in the step 4) is 60 ℃, the reaction time is 1.5h, and the grinding is performed by ball milling or mortar hand milling.